Polychloroalkylphosphonic acid salts



3,499,923 PGLYCHLQRGALKYLPHOSPHONTC ACID SALTS Henryk A. Cyba, Evanston,111., assignor to Universal Oil Products Company, Des Plaines, 111., acorporation of Delaware No Drawing. Filed Sept. 7, 1965, Ser. No.485,541 Int. Cl. C07c 69/40, 69/52, 69/60 US. Cl. 260485 6 Claims Thisinvention relates to a novel composition of matter and to the usethereof as an additive to organic substrates.

The novel composition of matter of the present invention is atrichloroalkylphosphonic acid salt of the condensation product of adialkanol amine and a polycarboxlic acid or anhydride thereof.

The condensation product of dialkanol amine and dicarboxylic acid oranhydride is prepared in any suitable manner. Any suitable dialkanolamine is used as a reactant and will be selected with reference to theultimate use of the salt. For example, when used, as an additive inlubricating oil or other organic substrates in which the additive isused in a concentration of greater than 1% the dialkanol amine is anN-aliphatic dialkanol amine and preferably an N-alkyldialkanol amine inwhich the alkyl group contains at least 10 and preferably from about 10to about 50 carbon atoms. However, when used as an additive in lowerconcentrations or for other uses, the alkyl group may contain a lessernumber of carbon atoms. Illustrative N-alkyldiethanol amines include N-methyl diethanolamine, N-ethyl diethanolamine, N- propyl-diethanolamine,N-butyl-diethanolamine, N-amyldiethanolamine, N-hexyl diethanolamine, Nheptyldiethanolamine, N octyl diethanolamine, N nonyldiethanolamine, N-decyl diethanolamine, N undecyldiethanolamine, N-dodecyl diethanolamine,N-tridecyldiethanolamine, N-tetradecyl-diethanolamine,N-pentadecyl-diethanolamine, N-hexadecyl-diethanolamine, N-heptarlecyl-diethanolamine, N-octadecyl-diethanolamine, N nonadecyldiethanolamine, N eicosyl diethanolamine, N henei cosyl diethanolamine,N docosyldiethanolamine, N tricosyl diethanolamine, N- tetracosyldiethanolamine, N- pentacosyl diethanolamine, N hexacosyldiethanolamine, N heptacosyl diethanolamine, N octacosyl diethanolamine,N nonacosyl diethanolamine, N triacontyl diethanolamine, etc.

It is understood that the N-aliphatic-diethanolamine may containaliphatic substituents attached to one or both of the carbon atomsforming the ethanol group. These compounds may be illustrated byN-aliphatic-dimethyl ethanolamine), N aliphatic di (l-ethylethanolamine)N-aliphatic di l-propylethanolamine) N-aliphatic di(l-butylethanolamine), N-aliphatic-di- (1 amyletlianolamine, N aliphaticdi (l hexylethanolamine), etc., N aliphatic di (2 methylethanolarnine),N aliphatic di (2 ethylethanolamine), N aliphatic di (2propylethanolamine), N aliphaticdi (2 butylethanolamine), N aliphatic di(2 amyl thanolamine), N aliphatic di (2 hexylethanolamine), etc. It isunderstood that these specific compounds are illustrative only and thatother suitable compounds containing the diethanolamine configuration maybe employed.

3,499,923 Patented Mar. 10, 1970 The specific compounds hereinbefore setforth are examples of N-aliphatic-diethanolamines. OtherN-aliphaticdialkanolamines include N aliphatic dipropanolamines andN-aliphatic-dibutanolamines, although N-aliphaticdipentanolamines,N-aliphatic-dihexanolamines and higher dialkanolamines may be used insome cases. It is understood that these dialkanolamines may besubstituted in a manner similar to that specifically describedhereinbefore in connection with the discussion of the. diethanolamines.Furthermore, it is understood that mixtures ofN-aliphatic-dialkanolamines may be employed, preferably being selectedfrom those hereinbefore set forth. Also, it is understood that thevarious dialkanolamines are not necessarily equivalent.

A number of N-alkyl-diethanolamines are available commercially and areadvantageously used in preparing the condensation product. For example,N-tallow-diethanolamine is available under the trade name of Ethomeen T/12. This material is a gel at room temperature, has an average molecularweight of 354 and a specific gravity at 25/25 C. of 0.916. The alkylsubstituents contain from about twelve to twenty carbon atoms per groupand mostly sixteen to eighteen carbon atoms. Another mixed product isavailable commercially under the trade name of Ethomeen S/ 12 and is N-soya-diethanolamine. It is a gel at room temperature, has an averagemolecular weight of 367 and a specific gravity at 25 /25 C. of 0.911.The alkyl substituents contain 16-18 carbon atoms per group. Stillanother commercial product is Ethomeen C/ 12, which is N-coco-diethanolamine, and is a liquid at room temperature, and has anaverage molecular Weight of 303 and a specific gravity at 25/25 C. of0.874. The alkyl groups contain mostly twelve carbon atoms per group,although it also contains groups having from eight to sixteen carbonatoms per group. Still another commercially available product isN-stearyl-diethanolamine, which is marketed under the trade name ofEthomeen 18/12. This product is a solid at room temperature, has anaverage molecular weight of 372 and a specific gravity at 25 /25 C. of0.959. It contains eighteen carbon atoms in the alkyl substituent.

Still another commercially available dialkanolamine is prepared by theoxyalkylation and more particularly by oxyethylation of beta-amines. Thebeta-amine is defined as an alkyl amine in which the nitrogen atom isattached to the second or beta carbon atom of the alkyl group. Acommercially available diethanolamine in this embodiment is N (1methyltetradecyl) diethanolamine and is marketed under the trade name ofEthomeen L-15/ 25. This diethanolamine has a melting point of about 50F., a neutralization equivalent of 373 and a specific gravity at 25 C.of 0.897. It is understood that other dialkanolamines containing thebeta configuration may be used. Illustrative examples include N l methylhexadecyl) diethanolamine, N (1 methyl heptadecyl)- diethanolamine, N-(lmethyl octadecyl) diethanolamine, N (l methyl nonadecyl) diethanolamine,etc., as well as corresponding dipropanolamines, dibutanolamines, etc.It is believed that these dialkanolamines may be of advantage inimparting to the final salt improved solubility in hydrocarbons andlower melting or softening points.

The N aliphatic dialkanolamine is reacted with a polycarboxylic acid.The polycarboxylic acid preferably comprises an aliphatic dicarboxylicacid. Illustrative dicarboxylic acids include oxalic, malonic, succinic,glutaric, adipic, pimelic, suberic, azelaic, sebacic, maleic, fumaric,itaconic, citraconic, mesaconic, etc. While the dicarboxylic acids arepreferred, it is understood that polycarboxylic acids containing three,four, or more carboxylic acid groups may be employed. Furthermore, it isunderstood that a mixture of polycarboxylic acids and particularly ofdicarboxylic acids may be used. A number of relatively inexpensivedicarboxylic acids comprising a mixture of these acids are marketedcommercially under various trade names, including VRl Acid, Dimer Acid,Empol 1022, etc., and these acids may be used in accordance with thepresent invention. For example, VR-l Acid is a mixture of dicarboxylicacids and has an average molecular weight of about 700, is a liquid at77 F., and has an acid number of about 150 and an iodine number of about36. It contains thirty-six carbon atoms per molecule.

Another preferred polycarboxylic acid comprises a mixed acid beingmarketed commercially under the trade name of Empol l022. This dimeracid is a dilinoleic acid and is represented by the following generalformula:

This acid is a viscous liquid, having an apparent molecular weight ofapproximately 600. It has an acid value of 180-192, an iodine value of80-95, a saponification value of 185195, a neutralization equivalent of290310, a refractive index at 25 C. of 1.4919, a specific gravity atl5.5/l5.5 C. of 0.95, a flash point of 530 F., a fire point of 600 F.,and a viscosity at 100 C. of 100 centistokes. The above-mentioned DimerAcid" is substantially the same as Empol l022.

While the polycarboxylic acid may be employed, advantages appear to beobtained in some cases when using anhydrides thereof and particularlyalkenyl-acid anhydrides. A preferred alkenyl-acid anhydride isdodecenylsuccinic anhydride. Other alkenyl-acid anhydrides includebutenyl-succinic anhydride, pentenyl-succinic anhydride,hexenyl-succinic anhydride, heptenyl-succinic anhydride,octenyl-succinic anhydride, nonenyl-succinic anhydride, decenyl-succinicanhydride, undecenyl-succinic anhydride, tridecenyl-succinic anhydride,tetradecenyl-succinic anhydride, pentadecenyl-succinic anhydride,hexadecenylsuccinic anhydride, heptadecenyl-succinic anhydride,octadecenyl-succinic anhydride, nonadecenyl-succinic anhydride,eicosenyl-succinic anhydride, etc. While the alkenyl-succinic anhydridesare preferred, it is understood that the alkyl-succinic anhydrides maybe employed, the alkyl groups preferably corresponding to the alkenylgroups hereinbefore specifically set forth. Similarly, while thealiphatic succinic anhydrides are preferred, it is understood that theanhydrides and particularly aliphaticsubstituted anhydrides of otheracids may be employed including, for example, adipic anhydride andparticularly aliphatic adiptic anhydrides, glutaric anhydride andparticularly aliphatic glutaric anhydrides, etc.

It is understood that the aliphatic substituents attached to the Naliphatic dialkanolamine and/or the polycarboxylic acid or anhydride maybe either of straight chain or branched chain configuration. Likewise,these aliphatic groups may be substituted by non-hydrocarbon groupsincluding those containing nitrogen, oxygen, halogen and particularlychlorine and bromine, etc.

The condensation of N aliphatic dialkanolamine and polycarboxylic acidor anhydride is effected in any suitable manner but will comprise theinter-reaction with the liberation of water, and also may include theformation of a polymeric compound. The reaction generally is effected ata temperature above about 175 F. and preferably at a higher temperature,which usually will not exceed about 400 F., although higher or lowertemperatures may be employed under certain conditions. The exacttemperature will depend upon whether a solvent is used and, whenemployed, on the particular solvent. For example, with benzene as thesolvent, the temperature will be of the order of 175 F, with toluene thetemperature will be of the order of 250 F, and with xylene the order of300320 F. Other preferred solvents include cumene, naphtha, Decalin,etc. Any suitable amount of the solvent may be employed but preferablyshould not comprise a large excess because this will tend to lower thereaction temperature and slow the reaction. Water formed during thereaction may be removed in any suitable manner including, for examp.e,by operating under reduced pressure, by removing an azeotrope ofwatersolvent, by distilling the reaction product at an elevatedtemperature, etc. A higher temperature may be utilized in order toremove the water as it is being formed. The time of reaction issufiicient to effect the desired reaction and, in general, will rangefrom about four to forty hours or more. Preferably one-half to two moleproportions of N aliphatic dialkanolamine are reacted with one moleproportion of acid.

The condensation product prepared in the above manner is reacted with atrichloroalkylphosphonic acid to form a salt. A preferredtrichloroalkylphosphonic acid is trichloromethylphosphonic acid, whichis available commercially, generally in the form of its monohydrate. Themonohydrate may be used in forming the salt of the present invention.Other acids include trichloroethylphosphonic acid,trichloropropylphosphonic acid, trichlorobutylphosphonic acid,trichloropentylphosphonic acid, trichlorohexylphosphonic acid, as wellas more highly chlorinated compounds as, for example, tetra, penta,hexa, or hepta chloroalkylphosphonic acids. Illustrative acids includepentachloroethylphosphonic acid, heptachloropropylphosphonic acid, etc.Here again it is understood that the hydrate of the acid may be used toprepare the salt of the present invention.

The salt is prepared in any suitable manner and generally by comminglingthe condensation product and acid, preferably with intimate stirring.Although the mixing may be effected at ambient temperature, generally itis preferred to heat the reaction mixture, usually at a temperature upto about 400 F. and preferably from about 175 to about 350 F. in orderto facilitate formation of the salt. However, heating to an excessivetemperature should be avoided in order to preclude chemical reactionbetween the acid and condensation product which would result inliberation of water, halogen or hydrogen halide.

In general the condensation product is used in a mole proportion of from1 to 2 moles thereof per 1 mole of acid. However, it is understood thatdifferent proportions may be used which may range from 0.5 to 2 moleproportions of the condensation product per 1 mole proportion of acid.Stated another way, the condensation product is used in a proportion offrom 0.5 to 2 basic equivalents per 1 acid equivalent of thetrichloroalkylphosphonic acid.

Although applicant does not wish to be limited thereto, it is believedthat the salt of the present invention will have the followingconfiguration. The specific configurations set forth below describe thetrichloromethylphosphonic acid salt of the condensation product ofdodecenylsuccinic anhydride and Ethomeen T/ 12.

where n is an integer of from one to 100 and preferably from one to 10.

The above formula, when n is one, illustrates the condensation productof one hydroxyl of the diethanolamine with one anhydride oxygen. It isunderstood that the other hydroxyl groups of the diethanolamine canreact with another anhydride molecule and/ or that the hydroxyl of thecarboxyl groups may react with another diethanolamine molecule. Thisproduces polyester type polymers which may be used in preparing thesalts of the present invention.

A generic formula of the salt of the present invention may berepresented by the following:

where R is an alkyl group of from 1 to 50 carbon atoms, R is an alkylenegroup of from 2 to 8 carbon atoms, X is the residual fragment of thepolycarboxylic acid, anhydride or further reaction product thereof, Y ishydrogen or COX, Z is the condensation product of the dialkanol amineand dicarboxylic acid or anhydride, n is an integer of from one to 100and preferably from one to 10, and m is zero or one.

The salt may be recovered as a solid or viscous liquid but generally isin the form of a grease-like product. The salt may be utilized as suchor dissolved in a suitable solvent and used in this manner. The solventwill be selected with reference to the use to be made of the salt. Whenthe salt is to be used as an additive to hydrocarbon oil, a suitablesolvent includes aromatic hydrocarbon and particularly benzene, toluene,ethylbenzene, cumene, or paraffin hydrocarbon including hexane, heptane,octane, nonane, etc., or mixtures containing one or both of these typesof hydrocarbons such as naphtha, gasoline, kerosene, etc.

The salt of the present invention will have varied utility including useas an additive to organic substrates which undergo oxidative, thermaland/ or other deterioration. Organic substrates include gasoline,naphtha, kerosene, jet fuel, lubricating oil, diesel fuel, fuel oil,residual oil, drying oil, grease, wax, resin, plastic, rubber, etc. Inlubricating oil, the additive functions as a lubricity or extremepressure agent. In addition, the additive serves as a flame-proofingagent, detergent-dispersant, peroxide decomposer, corrosion inhibitor,rust inhibitor, etc.

The salt of the present invention is advantageously used as an additivein lubricating oil. The lubricating oil may be of natural or syntheticorigin. The mineral oils include those of petroleum origin and arereferred to as motor lubricating oil, railroad type lubricating oil,marine oil, differential oil, diesel lubricating oil, gear oil, cylinderoil, specialty products oil, cutting oil, drawing oil, metal workinglubricant, etc. Other oils include those of animal, marine or vegetableorigin.

The lubricating oils generally have a viscosity within the range of from10 SUS at 100 F. to 1000 SUS at 210 F. (SAE viscosity numbers includethe range from SAE 10 to SAE 160). The petroleum oils are obtained fromparafiinic, naphthenic, asphaltic or mixed base crudes. When highlyparaffinic lubricating oils are used, a solubilizing agent also may beused if of advantage.

Synthetic lubricating oils are of varied types including aliphaticesters, polyalkylene oxides, silicones, esters of phosphoric and silicicacids, highly fluorine-substituted hydrocarbons. etc. Of the aliphaticesters di-(Z-ethylhexyl) sebacate is being used on a comparatively largecommercial scale. Other aliphatic esters include dialkyl azelates,dialkyl suberates, dialkyl pimelates, dialkyl adipates, dialkylglutarates, etc. Specific examples of these esters include dihexylazelate, di-(Z-ethylhexyl) azelate, di-3,5,5-

trimethylhexyl glutarate, di-3,5,5-trimethylpentyl glutarate,di-(Z-ethylhexyl) pimelate, di-(Z-ethylhexyl) adipate, triamyltricarballylate, pentaerythritol tetracaproate, dipropylene glycoldipelargonate, 1,5-pentanediol-di-(2- ethylhexanonate), etc. Thepolyalkylene oxides include polyisopropylene oxide, polyisopropyleneoxide diether, polyisopropylene oxide diester, etc. The siliconesinclude methyl silcone, methylphenyl silicone, etc., and the silicatesinclude, for example, tetraisooctyl silicate, etc. The highlyfluorinated hydrocarbons include fluorinated oil, perfluorohydrocarbons,etc.

Additional synthetic lubricating oils include (1) neopentyl glycolesters in which the ester group contains from three to twelve carbonatoms or more, and particularly neopentyl glycol propionates, neopentylglycol butyrates, neopentyl glycol caproates, neopentyl glycolcaprylates, neopentyl glycol pelargonates, etc., (2) trimethylol alkaneesters such as the esters of trimethylol ethane, trimethylol propane,trimethylol butane, trimethylol pentane, trimethylol hexane, trimethylolheptane, trimethylol octane, trimethylol nonane, trimethylol decane,trimethylol undecane, trimethylol dodecane, etc., and particularlytriesters in which the ester portions each contain from three to twelvecarbon atoms and may be selected from those hereinbefore specificallyset forth in connection with the discussion of the neopentyl glycolesters, (3) complex esters composed of dibasic acids and glycols,especially neopentyl, neohexyl, etc., glycols further reacted withmonobasic acids or alcohols to give lubricants of viscosities at 210 F.of from four to twelve centistokes or higher, and (4)tricresylphosphate, trioctylphosphate, trinonylphosphate,tridecylphosphate, etc., as well as mixed aryl and alkyl phosphates.

The present invention also is used in the stabilization of greases madeby compositing one or more thickening agents with an oil of natural orsynthetic origin. Metal base synthetic greases are further classified aslithium grease, sodium grease, calcium grease, barium grease, strontiumgrease, aluminum grease, etc. These greases are solid or semi-solid gelsand, in general, are prepared by the addition to the lubricating oil ofhydrocarbon soluble metal soaps or salts of higher fatty acids as, forexample, lithium stearate, calcium stearate, aluminum naphthenate, etc.The grease may contain one or more thickening agents such as silica,carbon black, talc, organic modified bentonite, etc., polyacrylates,amides, polyamides, aryl ureas, methyl N -n octa decyl terephthalomate,etc. Another type of grease is prepared from oxidized petroleum wax, towhich the saponifiable base is combined with the proper amount of thedesired saponifying agent, and the resultant mixture is processed to agrease. Other types of greases in which the features of the presentinvention are usable include petroleum greases, whale grease, woolgrease, etc., and those made from inedible fats, tallow, butchers waste,etc.

Oils of lubricating viscosity also are used as transmission fluids,hydraulic fluids, industrial fluids, etc., and the novel features of thepresent invention are used to further improve the properties of theseoils. During such use the lubricity properties of the oil are important.Any suitable lubricating oil which is used for this purpose is improvedby incorporating the additive of the present invention.

Oils of lubricating viscosity also are used as cutting oils, rollingoils, soluble oils, drawing compounds, etc. In this application, the oilis used as such or as an emulsion with water. Here again, it is desiredthat the oil serves to lubricate the metal parts of saws, knives,blades, rollers, etc., in addition to dissipating the heat created bythe contact of the moving metal parts.

Oils of lubricating viscosity also are used as slushing oils. Theslushing oils are employed to protect finished or unfinished metalarticles during storage or transportation from one area to another. Themetal articles may be of any shape or form including steel or othermetal sheets,

plates, panels, coils, bars, etc., which may comprise machine parts,engines, drums, pistons rings, light arms, etc., as well as farmmachinery, marine equipment, parts for military or other vehicles,household equipment, factory equipment, etc. A coating which may bevisible to the eye, or not, as desired, covers the metal part andprotects it from corrosion.

The salt of the present invention also is useful as an additive in fueloil to prevent sediment formation. The fuel oil is marketed undervarious names including fuel oil, furnace oil, burner oil, range oil,diesel oil, etc. In such use the salt prevents sediment formation whichmay be due to oxidation, thermal reactions, etc., and also serves todisperse any sediment which is formed in the oil. The salt also servesas a rust or corrosion inhibitor, as well as retarding discoloration ofthe oil.

In another embodiment the salts of the present invention possessinsecticidal properties with good inner-therapeutic action. They may beemployed against many types of mites and insects such as, for example,Corausius larvae, Cotoneaster aphid, apple aphid, black bean aphid, peaaphid, etc. The salt, preferably as a solution in a suitable solvent,may be used for the control of various larvae, mites, insects as flourbeetle, Mexican bean beetle, black carpet beetle, milkweed bug, Germancockroaches, southern army worms, mealy bug, sow bug, citrus red spider,greenhouse rcd spider, various mosquitoes, yellow fever mosquito,malarial mosquito, houseflies, etc.

As hereinbefore set forth, the salts of the present invention alsopossess flame-proofing or flame retardant properties and therefore, areuseful in plastics, coatings, paints, drying oils, etc., as well as infibrous materials. For example, in textiles, the salt imparts flameretardant as Well as fungicidal properties to the fabric.

The concentration of the salt to be employed as an additive will dependupon the particular substrate in which it is to be used. In general, theadditive is used in a concentration of from about 0.001% to about 25% byweight of the substrate and more specifically within the range of from0.01% to about by weight of the substrate. When used in conventionallubricating oil, the additive generally may be employed in aconcentration of from about 0.01% to about 2% by Weight of the oil. Whenused in lubricating oil for more severe operations, such as hypoid gearoil, the additive is used in a concentration of from about 1% to about20% or more by weight of the oil. In general, substantially the samerange of additive concentration is employed when the oil is used astransmission fiuid, hydraulic fluid, industrial fluid,

etc. When the oil is used in the formulation of a grease,

the additive is used in a concentration of from about 0.5% to 5% byweight of the oil. When used in cutting oil, rolling oil, soluble oil,drawing compound, etc., the additive may be used in a concentration offrom about 0.1% to about by weight of the oil. When used in slushingoil, the additive may be used in a concentration of from about 0.1% toabout by weight or more of the oil.

It is understood that the additive of the present invention may be usedalong with other additives incorporated in the organic substrate. Theother additives will depend upon the particular organic substrate. Forexample, in lubricating oil, the additional additives may comprise oneor more of viscosity index improvers, pour point depressors, anti-foamadditives, detergents, corrosion inhibitors, additional antioxidants,etc. Preferred additional antioxidants are of the phenolic type andinclude tertiarybutylcatechol, 2,6-ditertiarybuty1 4 methylphenol, 2,4-dimethyl-6-tertiarybutylphenol, etc., 2 tertiarybutvl 4- methoxyphenol,2-tertiary-4-ethoxyphenol, 3,3,5,5'-tetratertiarybutyl-dihydroxydiphenylmethane, etc.

The salt of the present invention is an emulsifying agent and thereforewill serve to emulsify water and oil of lubricating viscosity for use aslubricating oil, slushing oil, cutting oil, rolling oil, soluble oil,drawing compound, etc. When desired, an additional emulsifying agent maybe employed. Any suitable emulsifying agent can be used, includingalkali metal sulfonates of petroleum sulfonic acids, mahoganysulfonates, naphthenic acids, fatty acids, etc., fatty alcoholsulfonates, pentaerythritol oleates, laurates, etc. The amount of waterused in the emulsified oils will depend upon the particular use of theemulsion and may range from 0.25% to 50% or even up to 98% by weight ofthe composition.

The additive of the present invention is incorporated in the substratein any suitable manner and preferably is suitably agitated with orotherwise mixed in the substrate in order to obtain intimate dispersionof the additive in the substrate. When the substrate comprises a mixtureof two or more components, the additive of the present invention may becommingled with one of the components prior to mixing with the remainingcomponent or Components of the substrate.

The following examples are introduced to illustrate further the noveltyand utility of the present invention but not with the intention ofunduly limiting the same.

EXAMPLE I The salt of this example is the trichloromethylphosphonic acidsalt of the condensation product of dodecenylsuccinic anhydride andEthomeen T/ 12. As hereinbefore set forth, Ethomeen T/ 12 isN-tallow-diethanol amine in which the tallow group contains from 12 to20 carbon atoms and mostly 16 to 18 carbon atoms per group.

The condensation product was prepared by refluxing 141 g. (0.5 mole) ofdodecenyl-succinic anhydride with 192 g. (0.5 mole) of Ethomeen T/12 ing. of Decalin and 50 g. of xylene. The heating and refluxing werecontinued for a period of about 10 hours and a total of 10 cc. of Waterwere collected. Following completion of the reaction, the reactionmixture was distilled under water pumped vacuum at about 380 F. toremove solvent. The condensation product was analyzed and found to havea basic nitrogen content of 1.60 meq./ g. and a basic molecularequivalent Weight of 625.

The salt was prepared by commingling 10.87 g. (0.1 equivalent or 0.05mole) of trichloromethylphosphonic acid monohydrate with 62.5 g. (0.1basic equivalent) of the condensation product of dodecenyl-succinicanhydride and Ethomeen T/ 12 prepared as described above. The stirredmixture was heated to 195-212" F. and formed a homogeneous mixture. Themixture then was heated to about 265 F. to remove water which waspresent due to the use of the hydrate.

A 50% by weight solution of the salt in a commercial lubricating oil wasprepared by adding 73 g. of a com mercial lubricating oil to the saltprepared in the above manner and heating to about 250 F. with stirring.This resulted in a homogeneous solution, thereby demonstrating that thesalt was soluble in the lubricating oil.

EXAMPLE II The salt of the example is prepared by first forming thecondensation product of malei anhydride and Ethomeen T/l2 and thenreacting with trichloromethylphosphonic acid monohydrate.

The condensation product is prepared by refluxing 192 g. of EthomeenT/l2 (0.5 mole) and 49 g. (0.5 mole) of maleic anhydride in 200 g. ofxylene. The heating and refluxing is continued for about 12 hours,during which time about 8.5 cc. of water is collected.

The salt is prepared by comrningling, with stirring and heating, g.(0.25 mole) of the condensation product prepared in the above manner and78 g. (0.125 mole) of trichloromethylphosphonic acid monohydrate. Themixture is stirred and heated to a temperature of about 200 F. and thento a temperature of about 275 F. to remove water. The reaction mixtureis allowed to cool to room temperature and the salt may be used as suchbut preferably is formed as a solution in a suitable solvent.

9 EXAMPLE III The salt of this example is prepared by first forming thecondensation product of itaconic acid with Ethomeen C/l2 and thenreacting with trichloropropylphosphonic 10 In another series of teststhe machine was operated for five minutes at each load from 250 poundsto seizure at 250 pound increments. The maximum load and the time inminutes at this load to seizure are reported, as well as the temperatureof the oil. In this case the higher acid. The condensation product isprepared by heating and refluxing equal mole proportions of itaconicacid .temperaulre 1S P because means that the 011 and Ethomeen C/l2 inxylene solution. As hereinbefore 1S fg i g sailsfactflmly Eitemperatllre' set forth Ethomeen C/ 12 is N-coco-diethanol amine and e unCatm-g o1 l m 1S ex ample 1S dloctyl sebacate synthetic lubncatmg Oll.maiketed under the 1s a l1qu1d at room temperature, having an averagetrade name of Flex 01 201 lecular wei ht of 303 and containin an avera eof 12 mo g g Run No. 1 1n the following table 1s a run made using Farbonatoms alkyl group- T heatmg and refiuxln? the Plexol not containing anadditive and thus is the 1s continued until the theoretlcal amount ofwater 1s blank or control recovered- After Cooling to room temperature,an equal Run No. 2 is a run made using another sample of the moleProportion of tThlhloropfOPYIPhOSPhOIIiC acid is Plexol to which hasbeen added 4% by weight of the added to the condensation product and themixture is solution prepared as described in Example I (2% by mixed andheated to 180 F. to insure complete formaweight of active ingredient).

TABLE I Temperature, F. Torque, lbs. Wear, teeth Seizure conditions RunN0. 250 500 750 250 500 750 250 500 750 Load Time Ten ig 1 150 231 490-s3-4 9-10 1s-s 0 0 s 750 2 490 2 151 257 363 4-5 13 14 16-24 0 0 12 2,0002 600 S-Seizure tion of the salt. The salt is recovered in solution inthe From the data in the above table it will be seen that xylene solventand the solution is used as an additive the dioctyl sebacate withoutadditive (Run No. 1) underto organic substrates. went seizure at a loadof 750 pounds. In contrast, seizure EXAMPLE IV conditions for theexample of the dioctyl sebacate contaming the additive of the presentinvention was 2000 The Salt of this example is P p in substamlflnypounds. As another advantage to the additive of the t 5211116 manner asdescfibed in the Previous Preparatlohs present invention, the oil didnot undergo darkening durby first forming the condensation product ofN-decyling Run No. 2 dipropanol amine and dilinoleic acid and thenreacted 3 EXAMPLE 1 with trichloroethylphosphonic acid. For economicalreasons, the acid used in Empol 1022 which is available com- AnotherSenes P evaluatlons Was made In the am mercially. The properties of thisacid have been set forth P as flescrlhfid EXaInple V, except that thehereinbefore. The N-decyl-dipropanol amine and dilinoleic lubrlcatmg 011was 111196511 marketed cqmmerclally acid are heated and refluxed in thepresence of toluene 40 ,Carnes 340 Whlt? Typlcal Speclficatlons ofsolvent until the theoretical amount of water is liberated. O11 Includethe followmg:

The condensation product is then reacted With trich oro- Distillationrange F 740-975 ethylphosphonic acid, with stirring and heating, t fSpecific gravity at F. 0.8836 the salt. Viscosity:

EXAMPLE V At F. 360

At 210 F 52 2 As hereinbefore set forth the salt of the present inven-Flash 1" pomt, COC F 440 t1on is of special utility 1n lubr1cat1ng 011.One method Pour Oint F of evaluating lubricating oils is by the Falexmachine. R p "J efractlve index at 68 F 1.4805 This procedure isdescnbed 1n deta1l 1n a book entitled Sa bolt color +30 LubricantTesting authored by E. G. Ellis and published 50 y by ScientificPublications (Great Britain) Limited, 1953, Run No. 3 in the followingtable is a run using the pages -154. Briefly, the Falex machine consistsof a white oil not containing an additive and thus is the blank rotatingpin which runs between two V shape bearings or control run. which arespring loaded against the pin and provided Run No. 4 is a run usinganother sample of the white with means for varying the load. The oil tobe tested is 55 oil to which has been added 4% by weight of the saltpoured into a metal trough in which the pin and bearings solutionprepared as described in Example I (2% by are partly submerged. Themachine was operated for five Weight of active ingredient).

TABLE II Temperature, F. Torque, lbs. Wear, teeth Seizure conditions RunNo. 250 500 750 250 500 750 250 500 750 Load Time Tegng.

3 172 was as 30S s 425 0.1 275 4 164 277 41s 4-5 13-15 19-22 0 o 242,000 2 s50 SSeizure.

minutes each at 250 and 500 pound loads and then for Here again it willbe seen that the oil without additive forty-five minutes at 750 poundload. The data collected (Run No. 3) underwent seizure at a small load,in this includes the temperature of the oil and the torque at 0 case of425 pounds. In contrast, the oil containing the each of the loads, asWell as the wear which is determined by a ratchet wheel arrangement inwhich the teeth are advanced in order to maintain the desired load. Eachtooth is equivalent to approximately 0.000022 inch. Preferred additivesare those which impart low temperature, low torque and low wear to theoil.

additive of the present invention did not undergo seizure until a loadof 2000 pounds.

EXAMPLE VII The salt solution prepared as described in Example I 5 alsowas evaluated as a sediment inhibitor in fuel oil.

iii

This evaluation was made according to the Erdco test in which heated oilis passed through a filter and the time required to develop adifferential pressure across the filter of 25 in. Hg is determined. Itis apparent that the longer the time, the more effective is theadditive. However, with a very effective additive, the time to reach adifferential pressure across the filter of 25 in. Hg is lengthenedbeyond reasonable limits that the test is stopped after about 300minutes and the differential pressure at that time is reported.

In this evaluation, 0.001% by weight of the solution prepared asdescribed in Example I was incorporated in a commercial range oil andevaluated in the Erdco test. A differential pressure of only 0.4 in. Hgafter 300 minutes was developed, in contrast to a differential pressureof 25 in. Hg in less than 100 minutes for a sample of the oil notcontaining the additive.

EXAMPLE VIII The salt prepared as described in Example III is used in aconcentration of 1% by weight as an additive in grease. The additive isincorporated in a commercial Mid-Continent lubricating oil having anS.A.E. viscosity of 20. Approximately 92% of the lubricating oil then ismixed with approximately 8% by weight of lithium stearate. The mixtureis heated to about 450 F., with constant agitation. Subsequently, thegrease is cooled, While agitating, to approximately 248 F, and then thegrease is further cooled slowly to room temperature.

The stability of the grease is tested in accordance with ASTM D-942method, in which method a sample of the grease is placed in a bomb andmaintained at a temperature of 212 F. Oxygen is charged to the bomb, andthe time required for a drop of five pounds pressure is taken as theInduction Period. A sample of the grease without additive will reach theInduction Period in about eight hours. On the other hand, a sample ofthe grease containing 1% by Weight of the additive of the presentinvention will be of substantially higher stability.

I claim as my invention:

1. Polychloroalkylphosphonic acid salt of the condensation product ofdialkanol amine and polycarboxylic acid or anhydride thereof, saiddialkanol amine having from 2 to about 6 carbon atoms in each of thealkanol groups and said acid being selected from the group consisting ofoxalic, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic,sebacic, maleic, fumaric, itaconic, citraconic and mesaconic acids, saidsalt containing from 3 to 7 chlorine atoms and the alkyl group thereofcontaining from 1 to 6 carbon atoms.

2. The acid salt of claim 1 further characterized in that said dialkanolamine is an N-alkyl dialkanol amine having from 1 to carbon atoms in thealkyl group.

3. Trichloromethylphosphonic acid salt of the condensation product offrom I to 2 mole proportions of an N-alkyl diethanol amine in which saidalkyl group contains from 1 to 50 carbon atoms with a dicarboxylic acidor anhydride thereof, said acid being selected from the group consistingof oxalic, malonic, succinic, glutaric, adipic, pimelic, suberic,azelaic, sebacic, maleic, fumaric, itaconic, citraconic and mesaconicacids.

4. Trichloromethylphosphonic acid salt of the condensation product offrom 1 to 2 mole proportions of N-tallow diethanol amine with 1 moleproportion of polycarboxylic acid or anhydride thereof, said acid beingselected from the group consisting of oxalic, malonic, succinic,glutaric, adipic, pimelic, suberic, azelaic, sebacic, maleic, fumaric,itaconic, citraconic and mesaconic acids.

5. Trichloromethylphosphonic acid salt of the condensation product offrom 1 to 2 mole proportions of N-tallow diethanol amine withdodecenyl-succinic anhydride.

6. Trichloromethylphosphonic acid salt of the condensation product offrom 1 to 2 mole proportions of N-tallow diethanol amine with maleicanhydride.

References Cited UNITED STATES PATENTS 2,882,228 4/1959 Watson et a1.25056 LORRAINE A. WEINBERGER, Primary Examiner E. J. SKELLY, AssistantExaminer US. Cl. X.R.

